DE1568497A1 - Process for the preparation of isocyanates containing sulfonazide groups - Google Patents

Description

FARBENFABRIKEN BAYER AG LEVERKUSEN-Uyerwwfc. - ₀ u » _4ft * _A

Hb / ie »· March 1960

Process for the preparation of sulfonic azide groups containing

Isocyanates

The present invention relates to a process for the preparation of organic sulfonazide groups Mono- or polyisocyanates, in which primary mono- or polyamines containing sulfonazide groups are reacted with phosgene.

The reaction of amines with phosgene to form isocyanates is known per se. Several variants of these methods have already been described in detail.
(See Annalen 562 (1949), pages 75 - 136)

It is now very surprising that amines which contain one or more sulfonazide groups in the molecule can also be obtained from the corresponding amines by the action of phosgene. This is because it is known that azides are generally rapidly and completely decomposed by acids. The ready decomposition of azides at elevated temperatures is also known from the literature. However, under the conditions of the method according to the invention, which will be discussed in more detail below, both the amines containing azide groups and the isocyanates containing azide groups formed therefrom are not only relatively high

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Temperatures, but at the same time the action of acid, d. H. Exposed to hydrogen chloride. So it had to be on the ground of the prior art with a complete split of the Azide groups are expected under the process conditions. Contrary to these expectations, however, under the invention Process conditions decomposition reactions are not observed or only observed to a very minor extent, and sulfonic azide groups are obtained in very good yields containing isocyanates. These represent new connections. *

Suitable starting materials for the process according to the invention basically all primary mono- and polyamines that contain one or more sulfonic azide groups in the molecule. Amines of the general formula are particularly suitable for this purpose

(NO ₂ S) _n - R - (NH ₂ )

R denotes an organic radical which is derived from an alkane with 1-18 carbon atoms and a cycloalkane with 5-6 carbon atoms or an aromatic hydrocarbon, preferably derived from benzene, diphenyl, naphthalene and anthracene and m and η integers from 1-3. The organic radical R can carry further substituents that arise in the phosgenation

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reaction should behave inert, preferably alkyl, aryl, Aralkyl, alkoxy, aroxy, alkyl mercapto, aryl mercapto, Nitrile, sulfonic, carboxylic acid ester, sulfonic acid ester ^ Carboxamide and sulfonic acid amide radicals and halogen such as Chlorine or bromine.

The production of the usable as starting materials for Part of the new primary amines can be done, for example, by adding the corresponding amino or acylaminosulphonic acid chlorides with an aqueous solution of sodium azide, optionally in the presence of an organic solvent such as alcohol, acetone, dioxane, benzene or toluene and in the case of using acylaminosulfonic acid chlorides the protected amino group by saponification back into Freedom sets.

As examples of sulfonazide groups containing mono- and polyamines are:

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₂ N - CH ₂ - CH ₂ - SO ₂ N ₃ H ₂ N -

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HH ₂ // "\ - SO N

H ₂ N - CH ₂ - CH ₂ - CH ₂ - CH ₂ -

Cl ι

H ₂ N

SO ₂ N ₃

H ₂ N - CH ₂ - /

H ₂ N - </ A - CH ₂ - CH,

Cl -

NH,

H ₂ N -

CHpCH
<- ι - OCO 5 CH ₂ - - // \\ - SO ₂ N ₃ Cl - Cl NH ₂ f \ TT
υπ «
* SO ₂ N ₃ CH ₂ - OCO - ■ <

HoN - / ~ \ - SO ₀ N ₇

H ₂ N - # \ H ₂ N - 0% -

ei - / Ζ \ - ο -

NH

H ₂ N

Cl

0 (J 9 8 1 3/1 7 5

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Λ -

SO ₀ N,

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The conversion of the mono- or polyamines containing sulfonazide groups into the corresponding isocyanates is carried out by the customary technical methods of phosgenation, e.g. 1. by cold-phase-hot-phase phosgenation or by the hydrochloride or carbamate process, the corresponding amine hydrochlorides or carbamates being reacted with phosgene. The reaction conditions for the phosgenation can vary within certain limits. Hydrocarbons such as benzene, toluene, chlorobenzene or trichlorobenzene are preferably used as the reaction medium. But in special cases, other solvents, such as. B. nitrobenzene or tetramethylene sulfone, suitable. In order to achieve good yields, it is advisable not to choose the temperature during the phosgenation that is too high. For this reason, the cold phase-hot phase phosgenation is often to be preferred to the hydrochloride process, since in the first case the mixture of carbamide chloride and amine hydrochloride is obtained in such a fine suspension that the hot phosgenation is completed in a short time ^{at temperatures, among others, 10O 0 O.} The phosgenation can also be carried out continuously or batchwise.

Always performs the reaction of the invention with a large upper weft phosgene at temperatures between -20 and +200 ⁰ C, preferably -5 to +150 ⁰ C, whereby-one works with advantage in any of the solvents mentioned. -

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The process is exemplified using the conversion of 4-aminobenzenesulfonic acid azide into 4-isocyanatobenzenesulfonic acid azide explained as follows:

^N 3 ° 2 ^S "X7 - NH ₂ + COGl ₂ > ^H 2 ° 2 ^S '" ^ ~ ^{NC0 + 2 HC1}

The new mono- or polyisocyanates containing sulfonic azide groups represent distillable liquids, oils or crystalline substances depending on the type of amine used They should be used as intermediate products in the manufacture of pesticides and pharmaceuticals,

example 1
Production of-

a) Preparation of the starting material 233.5 parts of 4-acetylaminobenzenesulphonic acid chloride are dissolved in a solution of 70 parts of sodium azide in 800 parts of water with stirring and cooling at 2 - 3 ⁰ C entered. JE is stirred for 18 hours at room temperature, held for one hour at 40 ⁰ C and then filtered off with suction and washed with plenty of water. The moist paste is then stirred with 400 parts of 35% aqueous hydrochloric acid, and the mixture is heated to 95 ° C. over the course of 20 minutes, during which time everything dissolves. Daa crystallizes from the hot hydrochloric acid solution

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MA WI BAD ORIGINAL

Hydrochloride of 4-aminobenzenesulphonic acid azide on cooling. The free base is obtained from the hydrochloride in the usual way with aqueous soda solution as a rapidly solidifying oil. The yield is 159 parts with a melting point of 35-36 ^° C., that is 80 # of theory.

b) Method according to the invention

Ho parts of p-azidosulfonylaniline are dissolved in 200 parts of chlorobenzoJ. This solution is added dropwise at 0 C to a solution of 1üü parts of phosgene in 300 parts of chlorobenzene. The mixture is stirred overnight at 0 C and heats the resulting suspension while introducing phosgene at 60 - 70 ^0C. 60 - 70 ⁰ C as long as phosgene is introduced until the solution is clear and in the exhaust no more hydrogen chloride can be detected. The resulting clear, yellow solution is blown with pure nitrogen for four hours at 60 ° C. and evaporated in vacuo. 96 parts of crude p-azidosulfonyl-phenyl isocyanate remain in the residue in the form of a brown oil which crystallizes after standing for a short time at room temperature. The crystals are rubbed with a little petroleum ether, filtered off with suction and dried.
Yield: 72 parts of light gray crystals; Mp 40 - 41 ⁰ C; NCO content calc .: 1β, 75 #i found: 18.30 $>

Example 2

Production of N, O ₂ S -

^ iTCO

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a) Production of the starting material

232 parts of the sodium salt of 3-Acetylaminobenzolsulfonsäure chlorosulfonated in 750 parts of chlorosulfonic acid at 80 ⁰ C and discharged the Chlorsulfonierungsmischung 2200 parts of ice. The humid paste of 3-Acetylaminobenzolsulfonsäurechlorids as described in Example 1 (a) in 3-Aeetylaminobenzolsulfonsäureazid of melting point 109 - converted 110 ⁰ C and this is then as described there for 3-Aminobenzolsulfonsäureazid of melting point 61 - is saponified 62 ⁰ C. The yield is 130 parts, that's $ 66> of theory.

b) Method according to the invention

138 parts of 3-Azidosulfonyl-aniline are added at -5 ⁰ C to a solution of 220 parts of phosgene in 1000 parts of chlorobenzene. The resulting suspension is stirred overnight and then phosgenated further by the method described in Example 1b) and then blown out with nitrogen. When the resulting pale yellow solution is evaporated, 156 parts of crude 3-azidosulfonyl-phenyl isocyanate are obtained, which, after standing in the refrigerator for a short time, turns into a crystalline mass. The crystals are rubbed with petroleum ether, filtered off with suction and dried.

Yield: half parts of colorless crystals; Pp ^{37-39 0} C NCO content calc .: 18.75 #; found: 18.50 #.

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Example 3

Production of N ₃ O ₃ S - ^ A - NCO

CH ₃

a) Preparation of the starting material 209 parts of the sodium salt of 1-methyl-r2-aminobenzene-5-sulfonic acid are stirred with 450 parts of acetic anhydride and the mixture is melted together at 110.degree. After two hours at 11O ⁰ C the melt is poured out, crushed and stirred with methylene chloride, washed and dried.

The acetyl compound obtained (247 parts) is introduced into 800 parts of chlorosulfonic acid, the solution is kept for two hours at 60 ^° C. and two hours at 80 ^° C. and then applied to 3500 parts of ice. The precipitated sulfonic acid chloride is filtered off with suction and washed with plenty of water.

The moist sulfonic acid chloride paste is then introduced into a solution of 75 parts of sodium azide in 500 parts of water at 0 to +5 ° C., the mixture is stirred at room temperature for 18 hours, ^{kept at 40 °} C. for a further hour and the well-crystallized sulfonic acid azide is filtered off with suction and with Water washed.

The sulfonic acid azide obtained in this way is dissolved in 500 parts of boiling alcohol, the alcoholic solution with 150 parts 35% hydrochloric acid was added and the solution was boiled for 30 minutes.

After cooling to 0 to +5 ⁰ C the hydrochloride of the i-methyl-2-aminobenzolsulfonsäureazid is suctioned off and transferred into 500 parts of water with 50 parts of soda ash in the free base, which at 89 - 90 ⁰ C melts. The yield is 146 parts.

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The yield is 146 parts.

b) Invention Agemäases method

To the solution of 100 parts of phosgene and 800 parts of chlorobenzene, the solution of 96 parts of 1-methyl-2-aminobenzene-5-sulfonsäjireazid is added at 0 0 and the resulting white suspension is left to stand ^{at 0 0 for 12 hours.} The mixture is then slowly heated and a further 400 parts of phosgene are introduced. After four hours at 80 ° C., a clear, light yellow solution is formed, from which excess phosgene is removed by passing in nitrogen. The substance sought is obtained by evaporating this solution: the yield is 107 parts of colorless crystals. Mp 43-44 ⁰ C; NCO content: calculated: 17.6 found: 17.5

Example 4

Production of N ₅ O ₂ S- fi \ -NCO

Cl

a) Representation of the starting material

229.5 parts of the sodium salt of 1-chloro-2-aminobenzene-5-sulfonic acid are described in Example 3 under (a) in 1-chloro-2-aetylaminobenzene-5-sulfonic acid chloride, which is obtained from benzene in prisms with a melting point of 142 - 144 ⁰ C crystallizes, and this then converted into i-chloro-Z-acetylaminobenzene-S-sulfonic acid azide, which crystallizes from alcohol and melts at 93 95 ^{0 G}

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BATH ORIGINAL

_ ₁₂ _ 1 568Λ97

274.5 parts of 1-chloro-2-acetylamino-5-sulfonic acid azide in the form of an approximately 30% strength aqueous paste are dissolved in 1000 parts of hot alcohol, 300 parts of 35 ice hydrochloric acid are added and the solution is boiled for 30 minutes. On cooling to 0 - 5 ⁰ C to crystallize, 200 parts of i-chloro-S-^ -äminobenzol sulfonsäureazid of melting point 75 - 77 ° from G, which are 85 # of theory.

b) Method according to the invention

The solution of 105 parts of i-chloro ^ aminobenzene - ^ - sulfonsäureazid in 500 parts of chlorobenzene is poured at -5 ⁰ C to the solution of 100 parts of phosgene in 800 parts of chlorobenzene and stirred entatehende the suspension for 18 hours at 0 C. Then, at 150 parts of phosgene were passed in at 75-95 ° C. in 30 minutes. Excess phosgene is blown out of the clear solution with nitrogen, shaken with activated charcoal, filtered and the solvent is drawn off. The residue is recrystallized from methylene chloride / petroleum ether. A yield of 97 parts of the desired substance in yellowish white crystals of melting point 61-63 ⁰ O.
NCO content: calc. Lc-, Z ', found. 1p, d <.

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Claims (1)

Claim Process for the preparation of sulfonic azide groups containing organic mono- and polyisocyanates, characterized in that mono- and polyamines containing sulfonazide groups are used with phosgene. ^A 9929 L 398 13/1751